新颖无限三股螺旋钴配位聚合物{[Co(4,4'-bipyridine)(4,4'azobispyridine)_2(NCS)_2]·H_2O}_n的合成、结构和性质的研究(英文)

The novel complex {[Co(bipy)(azpy)2(NCS)2]· H2O}n (where bipy=4,4′ bipyridine, azpy=4,4′ azobisp yridine) has been synthesized and characterized by elemental analyses, IR, UV, thermal analyses, and variable temperature magnetic susceptibility. The crystal (C32H26CoN12OS2, Mr=717.70) belongs to the orthorhombic, space group Pnna, a=2.21312(16)nm, b=1.40403(10)nm, c=1.14237(8)nm, V=3.5497(4)nm3, Z=4, Dc=1.343g· cm- 3, μ =0.645mm- 1, F(000)=1476, and final R1=0.0691, wR2=0.1129 for 231 parameters and 1674 observed reflections [I >2.00σ (I)]. The Co(Ⅱ) atom is, in a distorted octahedral geometry, coordinated by six nitrogen atoms from two bridging bipy, two monodentate azpy, and two thiocyanate groups. The bridging ligand bipy links Co(Ⅱ) atoms to form the infinite “ rod" with terminal coordination azpy ligand acting as sidearms. Unprecedented three parallel interpenetrating two dimensional (4,4) networks and novel infinite triple helices are formed via hydrogen bonding interactions. CCDC: 155588.

Metal-directed Assembly of Two Distinct Coordination Polymers with 2,5-Furandicarboxylic Acid and 4,4'-Bipyridine

By using solvothermal method, two new metal coordination polymers based on 2,5-furandicarboxylic acid（H2FDA） ligand and 4,4＇-bipyridine（bipy）, [Cu（FDA）（4,4＇-bipy）（DMF）]n·solvent（1） and {[Zn（4,4＇-bipy）（FDA）（DMF）]·DMF}n（2）, were produced and characterized by single-crystal X-ray diffraction analyses, elemental analyses, IR and powder X-ray diffraction. Compound 1 crystallizes in monoclinic space group P21/c with a = 11.104（2）, b = 10.396（2）, c = 18.772（4） , β = 96.20（3）o, V = 2154.2（7） 3, Dc = 1.378 g/cm^3, C19H17 Cu N3O6, Mr = 446.90, F（000） = 916, μ（Mo Kα） = 1.05 mm^-1, Z = 4, R = 0.0691 and wR = 0.1341 for 3537 observed reflections（I 2σ（I））, and R = 0.1062 and w R = 0.1482 for all data. Compound 2 crystallizes in monoclinic space group C2/c with a = 29.779（6）, b = 9.6417（19）, c = 17.292（3）, β = 105.69（3）°, V = 4779.9（16） 3, Dc = 1.445 g/cm^3, C22H22N4O7 Zn, Mr = 519.81, F（000） = 2144, μ（Mo Kα）= 1.08 mm^-1, Z = 8, R = 0.0641 and w R = 0.1007 for 2985 observed reflections（I 2σ（I））, and R = 0.1028 and w R = 0.1112 for all data. Different coordination geometry of metal ions, square pyramid of Cu2＋ and trigonal bipyramid of Zn2＋, bring about different orientations of FDA2- ligands as well as 4,4＇-bipyridine ligands, and furthermore distinct assembly structures for 1 and 2. The thermal stabilities of 1 and 2 are also investigated.

Synthesis, Crystal Structure and Catalytic Activity of a Bimetallic Rhodium Complex with 1,5-Cyclooctadiene and 2,2'-Bipyridine

A new complex [Rh（COD）（2,2＇-bipy）]·[Rh（COD）Cl2]（COD = 1,5-cyclooctadiene, 2,2＇-bipy = 2,2＇-bipyridine） has been synthesized and characterized by elemental analyses, NMR and single-crystal X-ray diffraction. The complex crystallizes in triclinic system, space group P1 with a = 7.4782（14）, b = 10.1400（11）, c = 16.6982（14） , α = 103.494（11）, β = 91.996（13）, γ = 103.829（12）o, C26H32Cl2N2Rh2, Mr = 649.26, V = 1190.0（3）3, Dc = 1.812 g/cm3, Z = 2, F（000） = 652, μ（Mo Kα） = 1.629 mm-1, R = 0.0286 and w R = 0.0463 for 3718 observed reflections（I 2σ（I））. The complex was linked to form 1D chains by hydrogen bonding interaction（C–H···Cl）, and further to construct a 2D layer structure by π···π stacking interactions between the pyridine rings of 2,2＇-bipy ligands. The hydroformylation catalyzed by the title complex was also studied.

Synthesis and Crystal Structure of a Cu(Ⅱ) Complex with Reduced Schiff-base N-(2-Hydroxybenzyl)-D,L-alanine and 4,4'-Bipyridine

A new complex [Cu2（sala）2（H20）2（4,4＇-bipy）]＇H20 （sala = N-（2-hydroxybenzyl）- D,L-alaninate, 4,4＇-bipy = 4,4＇-bipyridine） has been synthesized and characterized by elemental analysis, IR spectroscopy, thermogravimetric analysis and single-crystal X-ray diffraction. The complex crystallizes in monoclinic system, space group C2/c with a = 42.44（3）, b = 10.416（8）, c = 15.487（13） ./k, fl = 97.455（14）°, C30H36Cu2N4O9, Mr = 723.71, V = 6789（9） A3, Dc = 1.416 g/cm3, Z = 8, F（000） = 2992, μ（MoKa） = 1.308 mm-1, R = 0.0493 and wR = 0.1004 for 4878 observed reflections （I 〉 2σ（I））. Structural analysis shows that each copper（II） atom displays a distorted square-based pyramidal coordination geometry with two oxygen atoms and one nitrogen atom from one N-（2-hydroxybenzyl）-D,L-alaninate, one nitrogen atom from 4,4＇-bipyridine ligand and one water molecule. 4,4＇-Bipyridine ligand bridges two Cu（II） ions to form a dinuclear compound. The molecular structure is extended into a one-dimensional wavy chain through hydrogen bonds. These 1D chains are further expanded into 2D networks through hydrogen bonds.

Fluorescence property of tris(2,2′-bipyridine)ruthenium(Ⅱ)dichloride immobilized in the gallery ofγ-zirconium phosphates

Tris （2, 2′-bipyridine） ruthenium （Ⅱ） （Ru（bpy）3^2＋） dichloride was successfully immobilized into the galleria of layered gamma zirconium phosphate （γ-ZrP） preintercalated by butyl amine（BA）. The compounds showed extended luminescence lifetime of about four times of unimmobilized metal complex.

Synthesis,Crystal Structure and Bioactivity of a Pd(Ⅱ) Complex with Demethylcantharate and 2,2′-Bipyridine

A novel crystal with the molecular formula [Pd（DCA）（bipy）]2 [Pd（bipy）Cl2 ]·6.75H2O was formed by PdCl2 with disodium demethylcantharate （Na2 （DCA）,DCA2= 7-oxa-bicyclo[2.2.1]heptane-2,3-bicarboxylate） and 2,2-bipyidine （bipy） through the hydrothermal method.The complex was characterized by elemental analysis and infrared spectroscopy.The structure of the complex was determined by single-crystal X-ray diffraction,which is of triclinic system,space group P1 with a=13.6818（7）,b=14.8426（8）,c=15.0043（8）,α=97.319（3）,β=92.521（3）,γ=105.776（2）°,V=2898.4（3） 3,Dc=1.545 g·cm-3,Z=1,F（000）=1420,S=0.852,the final R=0.0525 and wR=0.1777 for 13634 observer reflections （I〉2σ（I））.The binding reaction of the complex with ct-DNA and bovine serum albumin （BSA） was studied by fluorescence spectroscopy.The results indicated that the complex binds to ct-DNA via the partial intercalation.The binding constant K A of the complex interaction with BSA was 3.98×10 5 L·mol-1 and one binding site would be formed.The antiproliferative activity of the complex against human hepatoma cells （SMMC7721） in vitro is much higher than that of Na 2 （DCA）.

Effects of Direction of Bridging of Thiocyanato on the Dimension of Coordination Polymers: Synthesis, Characterization and Single-crystal X-ray Structure Determination of [Cd(4,4'-dm-2,2'-bpy)(NCS)_2]_n and [Cd(4,4'-dmo-2,2'-bpy)(NCS)_2]_n Coordination Pol

Two new cadmium（II）-thiocyanato coordination polymers with 4,4＇-dimethyl-2,2＇-bipyridine（4,4＇-dm-2,2＇-bpy） and 4,4＇-dimethoxy-2,2＇-bipyridine（4,4＇-dmo-2,2＇-bpy） as chelating ligands were synthesized and characterized by elemental analysis, IR and 1H NMR spectroscopy and X-ray crystallography. Thermal properties were also studied as well. These complexes have formed as [Cd（4,4＇-dm-2,2＇-bpy）（NCS）2]n（1） and [Cd（4,4＇-dmo-2,2＇-bpy）（NCS）2]n（2）. The coordination numbers of CdII in 1 and 2 are six（Cd N4S2）. Direction of bridging of thiocyanato anions in 1 and 2 created one- and two-dimensional coordination polymers, respectively. The supramolecular features in these complexes were guided and controlled by weak directional intermolecular interactions.

Synthesis and Structural Characterizations of Ternary Iron(Ⅱ)Mixed Ligand Complex:Low Cost Materialsas a Precursor for Preparation of Nanometric Fe_(2)O_(3) Oxide

The reaction of the ligands,ethylenediaminetetraacetic acid terasodium salt(Na 4EDTA)and N—N heterocyclic diamines like2,2’-bipyridine(bipy)with iron(Ⅱ)sulfate with 1∶2∶2 stoichiometric ratios form the mononuclear ternary complex of formulae,[Fe_(2)(EDTA)(bipy)2]at pH~7.The FTIR and Raman laser spectra of the iron(Ⅱ)complex show that 2,2’-bipyridine is present asa bidentate ligand and the ethylenediaminetetraacetic acid terasodium salt as monodentate carboxylate anion.The electronic spectra and magnetic moments data suggest the six coordination number.It has two iron(Ⅱ)centers in octahedral environments,which are interlinked by carboxylato-O atoms of ethylenediaminetetraacetate and by nitrogen atoms of the two 2,2-bipyridine ligands in a chelating mode.Thermal analysis study show thatiron(Ⅱ)complex containing EDTA and 2,2’-bipyridine on its thermalde composition form the corresponding Fe_(2)O_(3) oxide in nano size at the temperature range~475℃.The iron(Ⅱ)complex was performed as a convenient low cost precursor for the preparation of Fe_(2)O_(3) nanoparticles by the the thermal decomposition method.The iron(Ⅲ)oxide composition has been discussedusing FTIR,X-ray diffraction(XRD),transmission electron microscopy(TEM)and energy-dispersive X-ray spectroscopy(EDX).

Biological Evaluation of New Schiff Bases: Synthesized from 4-Amino-3,5-dimethyl-1,2,4-triazole, Phenathroline and Bipyridine Dicarboxaldehydes

Four new Schiff bases with promising anticancer activity have been synthesized from 4-amino-3,5-dimethyl-1,2,4-triazole and di-pyridyl-aldehydes. Structures have been established by various spectroscopic methods. The compounds were tested in vitro to study their cytotoxicity and anti-oxidative activity in human lung carcinoma (A549), breast carcinoma (BT549), prostate adenocarcinoma (PC3) and mouse preadipocytes (3T3-L1) cells. Compound 1 was found to increase Glutathione (GSH) level slightly in all four cell lines. Compound 4 showed better selectivity and cytotoxicity against both BT549 and A549 cells compared to the anticancer drug tamoxifen. With the exception of compound 4 which reduced GSH levels in A549 and BT549, all other compounds maintained GSH levels in comparison to their respective controls.

Synthesis, crystal structure and photophysical properties of a neodymium trifluoroacetate complex with 2,2'-bipyridine

The neodymium trifluoroacetate complexes were synthesized and characterized by single-crystal X-ray diffraction for [Nd（CF3COO）3·Bpy·（H2O）3]Bpy（1）,elemental and TG analysis,FT-IR spectra,and PL spectra for Nd（CF3COO）3·Bpy（2）（Bpy：2,2＇-bipyri-dine）.The most interesting feature of the crystal structure for 1 is that it comprises a coordinated 2,2＇-bipyridine molecule and an out-sphere 2,2＇-bipyridine molecule.At the same time,the C-O distances appeared average which indicates the three atoms of carboxylato forming elec-tron-conjugate system.Hydrogen bond and π-π-stacking link the binuclear to two-dimensional sheet.The optical spectra for 2 exhibited that the complex possessed typical Nd（III） ion absorption and photoluminescence emission.The emission cross-section of 4F3/2→4I11/2 fluores-cence transition（3.63×10-20 cm2） was comparable with some laser glasses,which indicated good radiative properties of this neodymium trifluoroacetate complex in liquid matrix.The thermal analysis indicated that it was quite stable to heat.

Photoelectrical performance of nanocrystalline TiO_2 film electrode sensitized by Ru(Ⅱ)-bipyridine complexes

Two kinds of Ru(Ⅱ)-bipyridine complexes, cis-di(thiocyanate)bis(2,2′-bipyridyl-4,4′-dicarboxylate) ruthenium(Ⅱ) and cis-di(thiocyanate)bis(2,2′-bipyridyl-3,3′-dicarboxylate) ruthenium(Ⅱ), were utilized as the sensitizers to the nanocrystalline TiO-2 film electrodes. Study shows that the two dyes have quite different sensitization properties due to the strong steric effect of carboxyl groups. In addition, the pretreatment to nanocrystalline TiO-2 film electrodes with TiCl-4 was investigated, which is an effective way to improve the photoelectric conversion performances of sensitized TiO-2 electrodes.

PHASE TRANSFER OF PROTON CATALYZED BY 2,2'-BIPYRIDINE

Basic 2,2’-bipyridine (Pk_b 9.63) can catalyze the phase transfer of proton at the water/nitrobenzene interface. Investigations of chronopotentiometry with cyclic linear current-scanning and cyclic voltammetry show that the catalytic transfer behavior is closely related to pH of the aqueous phase. In this work, the theoretical expression of the transfer potential and current at different pHs has been deduced from the exper-

Syntheses and Crystal Structures of Two Silver(Ⅰ) Complexes with Organic Carboxylic Acid and Bidentate N-donor Ligands

The title complexes（NH4）[Ag（dpe）（H2bptc）]（1） and Ag2（bpy）（ox）·7H2O（2） were synthesized via slow evaporation at room temperature,and characterized by elemental analysis and infrared spectra.The crystal of 1 crystallizes in triclinic,space group P1 with a = 8.3959（7）,b = 11.8088（12）,c = 12.8175（13） ,α = 85.507（2）,β = 79.245（1）,γ = 84.174（2）o,V = 1239.7（2） 3,Z = 2,C28H22AgN3O8,Mr = 636.36,Dc = 1.705 g/cm3,F（000） = 644 and μ（MoKα） = 0.874 mm-1.The final R = 0.0479 and wR = 0.1426 for 3632 observed reflections with I 〉2σ（I） and R = 0.0559 and wR = 0.1503 for all data.The crystal of 2 crystallizes in orthorhombic,space group Pnna with a = 17.2291（17）,b = 7.5289（6）,c = 21.369（2）,V = 2771.9（4） 3,Z = 4,C22H30Ag2N4O11,Mr = 742.24,Dc = 1.779 g/cm3,F（000） = 1488 and μ（MoKα） = 1.476 mm-1.The final R = 0.0648 and wR = 0.2058 for 1996 observed reflections with I 〉2σ（I） and R = 0.0769 and wR = 0.2192 for all data.X-ray diffraction reveals that in complexes 1 and 2,both 1,2-di（4-pyridyl）ethylene and 4,4＇-bipyridine act as typical bidentate N-donor ligands to link two Ag centers.3,3＇4,4＇-Biphenyltetracarboxylate and oxalate anions play the role of organic linkers and counter-ions to balance the cationic charge of AgI.The rich hydrogen-bonding interactions and ligand-unsupported Ag…Ag interactions as well as π-π stacking interactions contribute to the construction of three-dimensional sandwich-like frameworks.

Two Metal-organic Frameworks(MOFs) Assembled from One Asymmetric Semirigid Multicarboxylate Ligand:Syntheses and Crystal Structural Characterizations

Hydrothermal reactions between a new flexible multicarboxylate ligand of 3-（2-carboxy-phenoxy）-benzoic acid（H2L） and transitional metal cations of M2＋（M = Cu2＋,Ni2＋） in the presence of the secondary ligands of 1,10-phenanthroline（phen）,2,2＇-bipyridine（2,2？-bpy）,and 4,4＇-bipyridine（4,4＇-bpy） afford two novel coordination polymers Ni2（H2O）2L2（phen）（μ-4,4＇-bpy）（1） and CuIIL（2,2＇-bpy）（2）.Both compounds were characterized by X-ray crystallography.Crystal data of 1：C31H24N3NiO7,Mr = 609.24,monoclinic,space group P21/c,a = 17.560（8）,b = 10.528（5）,c = 30.613（15） ,V = 5659（5） 3,Z = 4,Dc = 1.430 g/cm3,F（000） = 502,μ = 0.739 mm-1,R = 0.0902,wR = 0.1346（I 2σ（I））,S = 1.002.Crystal data of 2：C24H16CuN2O5,Mr = 475.93,monoclinic,space group P21/n,a = 9.8904（13）,b = 11.0782（16）,c = 18.321（3） ,β = 11.0782（16）°,V = 1993.8（5） 3,Z = 4,Dc = 1.585 g/cm3,F（000） = 972,μ = 1.137 mm-1,R = 0.0433,wR = 0.0723（I 2σ（I）） and S = 1.004.Compound 1 displays a one-dimensional（1D） zigzag chain structure constructed from phen ligands and the deprotonated ligands of L2-,which further forms a ladder-shaped supramolecular architecture via the bridge of 4,4＇-bpy ligand.Complex 2 also possesses a ladder-shaped architecture based on the dinuclear CuII units.

Comparative study of the extraction selectivity of PFO-BPy and PCz for small to large diameter single-walled carbon nanotubes

Semiconducting single-walled carbon nanotubes(s-SWCNTs)are fascinating materials for future electronic and optical applications.Conjugated polymer wrapping is one of the most promising methods for mass production of high purity s-SWCNTs.However,its chiral selectivity is relatively inferior to other s-SWCNT production methods.In this paper,the chiral selectivity of two polymers,poly[(9,9-dioctylfluorenyl-2,7-diyl)-alt-co-(6,6′-{2,2′-bipyridine})](PFO-BPy)and poly[9-(1-octylonoyl)-9H-carbazole-2,7-diyl](PCz),which are representatives of widely used polyfluorene and polycarbazole families,respectively,were comparatively studied.Both polymers exhibited high selectivity for a subset of existing chiral species in each of the commercially available raw SWCNT materials(CoMoCAT,HiPco,and arc-discharge)which cover a diameter range of 0.6–1.8 nm.Less chiral species were selected by PFO-BPy from small diameter(<1 nm)raw SWCNT materials,while more from large diameter(>1.2 nm)raw materials.High chiral purity(6,5)(>99%)and(7,5)(>75%)solutions were extracted by PFO-BPy and PCz from CoMoCAT materials,respectively.The different chiral angle and diameter selections for different raw materials by both polymers were ascribed to their different geometrical structures and related polymer-tube interactions.Our work provides indispensable information for better understanding the mechanism of polymer wrapping method and improving extraction of single chirality sSWCNTs.